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Radical Chain-Growth Polymerization: Mechanism01:09

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The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this species into...
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Anionic Chain-Growth Polymerization: Mechanism01:04

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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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Actin Polymerization01:42

Actin Polymerization

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Actin polymerization occurs through the head-to-tail association of binding sites on monomeric actin or G-actin to form filamentous or F-actin. The polymerization can be divided into three phases ̶  nucleation, elongation, and steady-state phase.
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Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
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Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
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A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization.

Aleksandr V Zhukhovitskiy1, Ilia J Kobylianskii1, Andy A Thomas2

  • 1Department of Chemistry , University of California , Berkeley , California 94720 , United States.

Journal of the American Chemical Society
|April 10, 2019
PubMed
Summary
This summary is machine-generated.

Researchers developed new palladium initiators for controlled carbene polymerization. This breakthrough enables the synthesis of advanced polyolefins with tunable properties and well-defined structures.

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Area of Science:

  • Polymer Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Carbene polymerization offers a route to unique polyolefins not accessible via traditional olefin polymerization.
  • Achieving controlled and living carbene polymerization has remained a significant challenge in polymer science.

Purpose of the Study:

  • To develop novel initiators for controlled and quasi-living carbene polymerization.
  • To synthesize polyolefins with high molecular weights, narrow dispersities, and defined chain ends.
  • To investigate the mechanism of this new polymerization process.

Main Methods:

  • Utilized (π-allyl)palladium carboxylate dimers as initiators.
  • Polymerized ethyl diazoacetate, a carbene precursor.
  • Employed experimental and theoretical mechanistic analysis.
  • Synthesized block copolycarbenes.

Main Results:

  • Achieved controlled and quasi-living carbene polymerization with nearly quantitative yields.
  • Produced polymers with degrees of polymerization exceeding 100 and molecular weight dispersities of 1.2-1.4.
  • Generated polymers with well-defined and diversifiable chain ends.
  • Successfully synthesized block copolycarbenes exhibiting microphase segregation.
  • Elucidated a novel dinuclear mechanism for the polymerization process.

Conclusions:

  • Introduced a new class of palladium initiators for controlled carbene polymerization.
  • Demonstrated the ability to synthesize well-defined polyolefins and block copolymers.
  • Provided mechanistic insights into a novel dinuclear polymerization pathway.